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WO2002048024A2 - Procede de fabrication de trichlorosilane - Google Patents

Procede de fabrication de trichlorosilane Download PDF

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Publication number
WO2002048024A2
WO2002048024A2 PCT/EP2001/013496 EP0113496W WO0248024A2 WO 2002048024 A2 WO2002048024 A2 WO 2002048024A2 EP 0113496 W EP0113496 W EP 0113496W WO 0248024 A2 WO0248024 A2 WO 0248024A2
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
hydrogen chloride
reactor
residence time
trichlorosilane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2001/013496
Other languages
German (de)
English (en)
Other versions
WO2002048024A3 (fr
Inventor
Leslaw Mleczko
Sigurd Buchholz
Torsten Sill
Frank Becker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SolarWorld AG
Original Assignee
SolarWorld AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SolarWorld AG filed Critical SolarWorld AG
Priority to AT01270489T priority Critical patent/ATE267143T1/de
Priority to EP01270489A priority patent/EP1341722B1/fr
Priority to DE50102361T priority patent/DE50102361D1/de
Priority to AU2002217047A priority patent/AU2002217047A1/en
Priority to US10/450,457 priority patent/US20040047793A1/en
Publication of WO2002048024A2 publication Critical patent/WO2002048024A2/fr
Publication of WO2002048024A3 publication Critical patent/WO2002048024A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
    • C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
    • C01B33/10763—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane from silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/04—Hydrides of silicon
    • C01B33/043—Monosilane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof

Definitions

  • the present invention relates to a method for producing trichlorosilane.
  • Trichlorosilane HSiCl 3 is a valuable intermediate for the production of high-purity silicon, dichlorosilane H 2 SiCl 2 , silane SiEL »and adhesion promoters. Technically, different methods are used to manufacture it.
  • US-A-4,676,967 and CA-A-1,162,028 disclose processes for the production of high-purity silane and high-purity silicon, the conversion of metallurgical silicon with hydrogen and silicon tetrachloride to trichlorosilane taking place in a first step.
  • the reaction is carried out at temperatures of about 400 to 600 ° C and under increased pressure greater than 100 psi (6.89 bar).
  • the reaction under elevated pressure is necessary to increase the yield of trichlorosilane.
  • the disproportionation of trichlorosilane to silane takes place. This inevitably produces silicon tetrachloride, which is recycled and returned to the reaction with hydrogen and metallurgical silicon.
  • the silane produced can finally be thermally decomposed to ultrapure silicon and hydrogen.
  • the raw material used in the process described above is mostly silicon of metallurgical quality, which contains various other metallic elements as impurities (up to a percentage range). These impurities are worked up during the purification of the chlorosilane products and mostly separated off in the form of the chlorides by chemical or physical means. The resulting chlorine loss must therefore be replaced.
  • the use of hydrogen chloride lends itself to replacing this loss of chlorine in circulatory processes. The latter reacts in an exothermic reaction with silicon to form the products tirchlorosilane, silicon tetrachloride and hydrogen.
  • DE 33 03 903 A1 discloses a process for the preparation of trichlorosilane from silicon, in particular from contact materials containing residual silicon, the silicon being brought into contact with an anhydrous chlorine source, such as hydrogen chloride gas and / or chlorine gas, in the presence of silicon tetrachloride at an elevated temperature.
  • anhydrous chlorine source such as hydrogen chloride gas and / or chlorine gas
  • Hydrogen chloride gas and / or chlorine gas is preferably added in an amount of 10 to 99 mol%, particularly preferably about 28 to 44 mol%.
  • the reason for this is that the amount of chlorine present in the system, including bound chlorine, for example in the form of silicon tetrachloride, trichlorosilane, dichlorosilane and hydrogen chloride, does not decrease in such processes.
  • the high chlorine supply through the addition of hydrogen chloride leads to a stoichiometric increase in the silicon tetrachloride in the system.
  • the chlorine balance can only be balanced by the undesired removal of chlorine-containing species, such as silicon tetrachloride.
  • US-A-4,526,769 discloses the production of trichlorosilane from silicon, silicon tetrachloride, hydrogen and hydrogen chloride in a two-stage process. In the first stage, the reaction takes place at high temperatures of 550-700 ° C according to:
  • the selectivity for the products silicon tetrachloride and trichlorosilane in this reaction depends strongly on the reaction temperature during the two stages. With increasing reaction temperature, SiCL »is predominantly formed.
  • the temperature must therefore be kept constant, especially in the second stage, within a comparatively small tolerance range.
  • Both stages are charged with educt silicon, the different temperatures that are achieved by a heat exchanger system are used to obtain a suitable product distribution. Disadvantages of the process described above are the complex construction of the two stages and the complicated expenditure for regulation and reaction control, in particular for maintaining the necessary temperatures.
  • the invention relates to a process for the preparation of trichlorosilane by reacting silicon with silicon tetrachloride and hydrogen with the addition of hydrogen chloride, characterized in that the residence time of the hydrogen chloride material in the reaction chamber 10 "3 to 50% of the residence time of the silicon tetrachloride.
  • the residence time of a component is understood to be the quotient of the reactor volume and the volume flow of the corresponding component (hydrogen chloride or silicon tetrachloride).
  • Silicon tetrachloride is not formed until the hydrogen chloride has a longer residence time and / or at higher temperatures. For this reason it is possible to achieve a significant increase in the yield of trichlorosilane through the short residence time of the chlorine-containing gas to be observed according to the invention.
  • the reaction space is understood to mean the area of the reactor in which silicon is present and whose reaction with the educts silicon tetrachloride and hydrogen takes place.
  • the residence time of the hydrogen chloride in the reaction space is preferably 10 -3 to 20% of the residence time of the silicon tetrachloride, particularly preferably 10 -3 to 5%.
  • Hydrogen chloride is preferably used in anhydrous form as the hydrogen chloride gas, it also being possible to use a mixture of hydrogen chloride gas and an inert gas, for example argon.
  • 0.05-20% by weight, preferably 0.1-10% by weight, of hydrogen chloride, based on the mass of the silicon tetrachloride supplied, is used.
  • the residence time of the hydrogen chloride in the reaction space according to the invention can be adjusted, for example, by feeding silicon tetrachloride and hydrogen into the reaction space from below via a gas distributor, while the hydrogen chloride is being fed in via a second gas supply device which is located in the upper part of the reaction space or the reactor ,
  • Hydrogen chloride is preferably fed in via a second gas supply device in the upper third of the reaction space.
  • Another possibility to set the residence time is to carry out the addition of hydrogen chloride at positions in the reactor where the gas velocity is very high. This is the case, for example, in a solids-separating cyclone or solids separator which is located behind or above the reactor or in a region of the return of the material separated in the cyclone or solids separator.
  • the residence time of the hydrogen chloride can be added at a point at which the discharged from the fluidized bed Material from the gas stream is separated (cyclone or solid separation) can be set.
  • the process according to the invention is carried out, for example, at pressures of 1 to 150 bar, preferably 10 to 60 bar, particularly preferably 25 to 40 bar.
  • temperatures from 350 to 800 ° C, preferably from 400 to 700 ° C, particularly preferably from 500 to 650 ° C.
  • the choice of the reactor in which the reaction according to the invention is to take place is not critical as long as the reactor has sufficient stability under the reaction conditions and allows the starting materials to come into contact.
  • work can be carried out in a fixed bed reactor, a rotary tube furnace or a fluidized bed reactor. Reaction control in a fluidized bed reactor is preferred.
  • the reaction of silicon with silicon tetrachloride, hydrogen and hydrogen chloride is particularly preferably carried out in a reactor in which the supplied gas flows through the silicon particles in such a way that the particles are fluidized and a fluidized bed is formed.
  • the inflow speed of the supplied gas must at least correspond to the loosening speed.
  • Loosening speed is understood to mean the speed at which a gas flows through a bed of particles and below which the fixed bed is retained, i.e. below which the bed particles remain largely stationary. Above this speed the fluidization of the bed begins, i.e. the bed particles move and the first bubbles form.
  • the inflow speed of the supplied gas is one to ten times, preferably one and a half to five times, the loosening speed.
  • a catalyst when carrying out the process according to the invention. Suitable catalysts are, for example, copper, copper oxide, mixed copper oxide, iron, iron (II) chloride, iron oxides, nickel, nickel chloride, nickel oxide.
  • Suitable catalysts are, for example, copper, copper oxide, mixed copper oxide, iron, iron (II) chloride, iron oxides, nickel, nickel chloride, nickel oxide.
  • the amount of catalyst used is, for example, 0.1 to 20% by weight, preferably 0.3 to 7.5% by weight, based on the amount of silicon.
  • metallurgical silicon is understood to mean silicon which can contain up to about 3% by weight of iron, 0.75% by weight of aluminum, 0.5% by weight of calcium and other impurities which are usually found in silicon. which was obtained by carbothermal reduction of silicon.
  • Silicon with a total content of secondary constituents and impurities of up to 20% by weight is particularly preferably used.
  • Silicon in the form of largely spherical silicon particles is particularly preferably used.
  • Highly pure trichlorosilane is preferably produced by the process according to the invention.
  • the starting materials also have the highest possible purity.
  • Hydrogen and silicon tetrachloride can be used, for example, in a molar ratio of 0.6: 1 to 5: 1, preferably 0.6: 1 to 4: 1, particularly preferably 0.6: 1 to 3: 1.
  • the trichlorosilane produced by the process according to the invention can be used, for example, for the production of silane and / or high-purity silicon.
  • the method according to the invention is preferably integrated into an overall method for producing ultrapure silicon.
  • the starting gas composition was 96% by volume of N 2 to 4% by volume of hydrogen chloride.
  • the feed gas composition was added a) via a gas distributor in the reactor base and b) via a second gas distributor 1 cm below the expanded height of the fluidized bed.
  • Example 1 shows that the selectivity for trichlorosilane in the reaction of silicon with hydrogen chloride increases significantly with decreasing residence time of hydrogen chloride in the reaction space.
  • the molar ratio H 2 / SiCL was 2 in the presence of 20% by volume of N 2 and the addition of 4% by volume of hydrogen chloride.
  • the H 2 / SiCl 4 mixture was added via a gas distributor in the reactor floor.
  • the hydrogen chloride was added a) likewise via the gas distributor in the reactor base and b) via a second gas distributor 1 cm below the expanded height of the fluidized bed.
  • a total yield of trichlorosilane of 9.4% (based on the amount of Cl introduced into the reactor) was obtained with a hydrogen chloride conversion of 95%.
  • the addition of hydrogen chloride in the upper part of the reaction space means that the overall yield of trichlorosilane increases to 11.4% (based on the amount of Cl introduced into the reactor), while the hydrogen chloride conversion only drops slightly to 80% ,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de fabrication de trichlorosilane consistant à faire réagir du silicium avec du tétrachlorure de silicium et de l'hydrogène, avec addition de chlorure d'hydrogène, le temps de séjour du chlorure d'hydrogène dans la chambre de réaction étant plus faible que le temps de séjour du tétrachlorure de silicium.
PCT/EP2001/013496 2000-12-14 2001-11-21 Procede de fabrication de trichlorosilane Ceased WO2002048024A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT01270489T ATE267143T1 (de) 2000-12-14 2001-11-21 Verfahren zur herstellung von trichlorsilan
EP01270489A EP1341722B1 (fr) 2000-12-14 2001-11-21 Procede de fabrication de trichlorosilane
DE50102361T DE50102361D1 (de) 2000-12-14 2001-11-21 Verfahren zur herstellung von trichlorsilan
AU2002217047A AU2002217047A1 (en) 2000-12-14 2001-11-21 Method for producing trichlorosilane
US10/450,457 US20040047793A1 (en) 2000-12-14 2001-11-21 Method for producing trichlorosilane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10062413.8 2000-12-14
DE10062413A DE10062413A1 (de) 2000-12-14 2000-12-14 Verfahren zur Herstellung von Trichlorsilan

Publications (2)

Publication Number Publication Date
WO2002048024A2 true WO2002048024A2 (fr) 2002-06-20
WO2002048024A3 WO2002048024A3 (fr) 2003-03-27

Family

ID=7667187

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/013496 Ceased WO2002048024A2 (fr) 2000-12-14 2001-11-21 Procede de fabrication de trichlorosilane

Country Status (6)

Country Link
US (1) US20040047793A1 (fr)
EP (1) EP1341722B1 (fr)
AT (1) ATE267143T1 (fr)
AU (1) AU2002217047A1 (fr)
DE (2) DE10062413A1 (fr)
WO (1) WO2002048024A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011015560A1 (fr) * 2009-08-04 2011-02-10 Schmid Silicon Technology Gmbh Procédé et installation de production de trichlorosilane
CN102642812A (zh) * 2012-04-11 2012-08-22 中国恩菲工程技术有限公司 从还原尾气中回收氯化氢的系统
WO2019068335A1 (fr) * 2017-10-05 2019-04-11 Wacker Chemie Ag Procede de preparation de chlorosilanes
WO2020125955A1 (fr) * 2018-12-18 2020-06-25 Wacker Chemie Ag Procédé de préparation de chlorosilanes
WO2020125944A1 (fr) * 2018-12-18 2020-06-25 Wacker Chemie Ag Procédé de préparation de chlorosilanes
WO2020221421A1 (fr) * 2019-04-29 2020-11-05 Wacker Chemie Ag Procédé pour la production de trichlorosilane comprenant des particules de silicium à structure optimisée

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006050329B3 (de) * 2006-10-25 2007-12-13 Wacker Chemie Ag Verfahren zur Herstellung von Trichlorsilan
DE102008017304A1 (de) * 2008-03-31 2009-10-01 Schmid Silicon Technology Gmbh Verfahren und Anlage zur Herstellung von Reinstsilizium
US8178051B2 (en) * 2008-11-05 2012-05-15 Stephen Michael Lord Apparatus and process for hydrogenation of a silicon tetrahalide and silicon to the trihalosilane
AU2012261522B2 (en) * 2008-11-05 2015-02-05 Lord Ltd. Lp An apparatus and process for hydrogenation of a silicon tetrahalide and silicon to the trihalosilane
US8298490B2 (en) * 2009-11-06 2012-10-30 Gtat Corporation Systems and methods of producing trichlorosilane
US20110243825A1 (en) * 2010-03-30 2011-10-06 Peak Sun Silicon Corporation Tetrahalosilane converter
KR101899611B1 (ko) * 2010-09-27 2018-09-17 지티에이티 코포레이션 가열기 및 이를 위한 관련 방법
EP2654912B1 (fr) 2010-12-20 2016-04-20 MEMC Electronic Materials, Inc. Fabrication de silicium polycristallin dans procédés à boucle sensiblement fermée qui entraînent des opérations de dismutation
WO2015089214A1 (fr) * 2013-12-10 2015-06-18 Summit Process Design, Inc. Procédé de production de trichlorosilane
US11027979B2 (en) 2016-11-23 2021-06-08 Wacker Chemie Ag Process for hydrogenating silicon tetrachloride
CN109694077B (zh) * 2017-10-24 2021-04-06 新特能源股份有限公司 一种四氯化硅转化为三氯氢硅的装置和方法

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
CA1162028A (fr) * 1979-08-01 1984-02-14 Larry M. Coleman Silane ultra-pur et obtention de silicium
JPS5673617A (en) * 1979-11-17 1981-06-18 Osaka Titanium Seizo Kk Manufacture of trichlorosilane
DE3024319C2 (de) * 1980-06-27 1983-07-21 Wacker-Chemitronic Gesellschaft für Elektronik-Grundstoffe mbH, 8263 Burghausen Kontinuierliches Verfahren zur Herstellung von Trichlorsilan
US4526769A (en) * 1983-07-18 1985-07-02 Motorola, Inc. Trichlorosilane production process
US5176892A (en) * 1990-12-06 1993-01-05 Dow Corning Corporation Supported metal catalyzed production of tetrachlorosilane

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011015560A1 (fr) * 2009-08-04 2011-02-10 Schmid Silicon Technology Gmbh Procédé et installation de production de trichlorosilane
CN102642812A (zh) * 2012-04-11 2012-08-22 中国恩菲工程技术有限公司 从还原尾气中回收氯化氢的系统
EP3858788A1 (fr) * 2017-10-05 2021-08-04 Wacker Chemie AG Procédé de préparation de chlorosilanes
CN111201198A (zh) * 2017-10-05 2020-05-26 瓦克化学股份公司 制备氯硅烷的方法
WO2019068335A1 (fr) * 2017-10-05 2019-04-11 Wacker Chemie Ag Procede de preparation de chlorosilanes
CN111201198B (zh) * 2017-10-05 2023-02-17 瓦克化学股份公司 制备氯硅烷的方法
US11643330B2 (en) 2017-10-05 2023-05-09 Wacker Chemie Ag Method for producing chlorosilanes
WO2020125955A1 (fr) * 2018-12-18 2020-06-25 Wacker Chemie Ag Procédé de préparation de chlorosilanes
WO2020125944A1 (fr) * 2018-12-18 2020-06-25 Wacker Chemie Ag Procédé de préparation de chlorosilanes
TWI723676B (zh) 2018-12-18 2021-04-01 德商瓦克化學公司 生產氯矽烷的方法
KR20210053986A (ko) * 2018-12-18 2021-05-12 와커 헤미 아게 클로로실란을 제조하는 방법
KR102607348B1 (ko) 2018-12-18 2023-11-29 와커 헤미 아게 클로로실란을 제조하는 방법
US12129177B2 (en) 2018-12-18 2024-10-29 Wacker Chemie Ag Process for preparing chlorosilanes
US12180079B2 (en) 2018-12-18 2024-12-31 Wacker Chemie Ag Process for preparing chlorosilanes
WO2020221421A1 (fr) * 2019-04-29 2020-11-05 Wacker Chemie Ag Procédé pour la production de trichlorosilane comprenant des particules de silicium à structure optimisée

Also Published As

Publication number Publication date
WO2002048024A3 (fr) 2003-03-27
EP1341722B1 (fr) 2004-05-19
EP1341722A2 (fr) 2003-09-10
AU2002217047A1 (en) 2002-06-24
US20040047793A1 (en) 2004-03-11
DE50102361D1 (de) 2004-06-24
ATE267143T1 (de) 2004-06-15
DE10062413A1 (de) 2002-07-04

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